Hollywood’s most storied modern couple only appeared together twice in the movies. The first time, in 2005’s “Mr. & Mrs. Smith,” they fell in love. A decade later, “By the Sea” would come just a year before their relationship would come to an end with Jolie Pitt filing for divorce. Both times they played a childless husband and wife whose passion had turned to resentment.

Their real life together was full of public declarations and displays of love, children, philanthropy, humanitarian work and glamour. In the movies, though, their surface beauty was only a mask for the rot and boredom underneath. Still, even through tears and gunfire, they always smoldered.

“You can absolutely madly love the same person you want to kill,” Jolie Pitt said in 2015, seated on a silk-sheeted bed next to Pitt on the set of “By the Sea,” filmed on their technical honeymoon, but it could have easily been about either. In “Mr. & Mrs. Smith,” they are actually trying to kill each other after all.

It was a strange story to fall in love to, but not uncommon in the entertainment business, even if Pitt was married at the time to Jennifer Aniston. Jolie had already been married twice, to Billy Bob Thornton and Jonny Lee Miller.

“We just became kind of a pair. And it took until, really, the end of the shoot for us, I think, to realize that it might mean something more than we’d earlier allowed ourselves to believe,” Jolie Pitt told Vogue in 2006.

Last week’s divorce filing comes after 12 years together and two in marriage. The couple wed in August 2014, privately at their French chateau in the Provence hamlet of Correns with their children serving as ring bearers and throwing flower petals.

An attorney for Jolie Pitt, Robert Offer, said that her decision was made “for the health of the family.” She is petitioning for physical custody of 15-year-old Maddox, 12-year-old Pax, 11-year-old Zahara, 10-year-old Shiloh, and 8-year-old twins Knox and Vivienne, with visitation rights for Pitt, who said in a statement to People how “saddened” he is.

“What matters most now is the wellbeing of our kids,” Pitt said, requesting space for the children.

The gossipy, tabloid origins would always at least partially define “Brangelina.” But after the media upheaval, Jolie Pitt and Pitt eventually settled into their own unique kind of globe-trotting domesticity. They were seldom-seen Hollywood royalty, their image predicated more on parenting than partying.

The pair adopted children from Cambodia, Vietnam and Ethiopia. In 2006, they formed the Jolie-Pitt Foundation, to which they funneled many of the millions they made selling personal pictures to celebrity magazines.

Jolie Pitt, who became special envoy for the United Nations in 2012, was an outspoken voice for refugees, as well as for breast cancer treatment after undergoing a double mastectomy herself. Pitt built homes in New Orleans for victims of Hurricane Katrina.

Both expanded creatively, too, but mostly separately, Jolie Pitt as a burgeoning and ambitious director of both war epics like “Unbroken,” and languid melodramas like “By the Sea,” and Pitt as a producer of socially relevant films through his Plan B production company, including the Academy Award-winning “12 Years a Slave,” last year’s “The Big Short” and the recently debuted festival hit “Moonlight.”

“By the Sea,” which Jolie Pitt wrote while grieving for her mother, who died in 2007, was sold nonetheless as the big on screen reunion of the couple who changed tabloid culture and our expectations of what exactly is possible on a movie set just 10 years earlier. But it fizzled with critics and audiences, making a mere $538,000 at the box office domestically. The “Mr. & Mrs. Smith” spark that enveloped its own stars and titillated audiences to the tune of $186.3 million domestically had given way to something infinitely more real.

“When we first worked together it was very different because we didn’t really know each other and we were young and, it was really a fun film, so we thought, maybe ‘By the Sea’ was going to be that kind of fun, but realized very quickly that it wasn’t,” Jolie Pitt told The Telegraph in 2015. “Then we joked that this is what happens after 10 years of marriage.”